CN103386313A - Double-treatment cleaning and regenerating method for vanadium-titanium based denitration catalyst - Google Patents
Double-treatment cleaning and regenerating method for vanadium-titanium based denitration catalyst Download PDFInfo
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- CN103386313A CN103386313A CN2013103395272A CN201310339527A CN103386313A CN 103386313 A CN103386313 A CN 103386313A CN 2013103395272 A CN2013103395272 A CN 2013103395272A CN 201310339527 A CN201310339527 A CN 201310339527A CN 103386313 A CN103386313 A CN 103386313A
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Abstract
The invention discloses a double-treatment cleaning and regenerating method for a vanadium-titanium based denitration catalyst and aims to solve the technical problem that the regenerating effect of the traditional vanadium-titanium based denitration catalyst is not so good. According to the technical scheme, the double-treatment cleaning and regenerating method comprises the following steps of: introducing air-ozone mixed gas into a catalyst regenerating reactor, and carrying out oxidation treatment to obtain a regenerated vanadium-titanium based denitration catalyst; then, placing the regenerated vanadium-titanium based denitration catalyst into a catalyst activity liquid, dipping the regenerated vanadium-titanium based denitration catalyst for 4-6h, then, taking out the regenerated vanadium-titanium based denitration catalyst, drying the regenerated vanadium-titanium based denitration catalyst in dry air at 50-60 DEG C for 1-3h, and then, repeating the operation once; and then, roasting the regenerated vanadium-titanium based denitration catalyst at the temperature of 160-200 DEG C for 1-3h, and then, roasting the regenerated vanadium-titanium based denitration catalyst at the temperature of 300-400 DEG C for 1-3h to obtain the cleaned and regenerated vanadium-titanium based denitration catalyst. The double-treatment cleaning and regenerating method has the beneficial effects that the denitration ratio of the regenerated vanadium-titanium based denitration catalyst can be up to 87%, so that efficient regeneration is realized, meanwhile, the conversion ratio of SO2/SO3 is effectively reduced, and the denitration cost is greatly reduced.
Description
Technical field
The invention belongs to the denitrating catalyst technical field, relate to a kind of renovation process of denitrating catalyst, particularly a kind of two cleaning and regeneration methods of processing of vanadium titanium based denitration catalyst.
Background technology
It is an importance of air contaminant treatment technology that nitrogen oxide is controlled, the SCR(SCR) denitration technology is remarkable to the removal effect of nitrogen oxide, is present most widely used gas denitrifying technology.In whole SCR denitrating system, catalyst is core component, V
2O
5-WO
3/ TIO
2It is a kind of catalyst for denitrating flue gas of main flow of large usage quantity, but in use find, because the fly ash content in coal-fired plant flue gas is generally higher, after flue gas enters the SCR reactor, import and export surface, vanadium titanium based denitration catalyst surface, internal steel body structure surface at reactor can form carbon deposit in various degree, cause the denitration performance of vanadium titanium based denitration catalyst to descend, the mode of processing carbon deposit commonly used is the method for making charcoal, but because ignition temperature is too high, so easily damage vanadium titanium based denitration catalyst., when denitration performance drops to while not reaching the denitration requirement, will change vanadium titanium based denitration catalyst.Because the cost of vanadium titanium based denitration catalyst is higher, thus generally can regenerate to the vanadium titanium based denitration catalyst that changes, to save the denitration cost.Commonly used is with ozone, vanadium titanium based denitration catalyst tentatively to be regenerated now, although the carbon deposit on vanadium titanium based denitration catalyst surface can be removed, the activity of vanadium titanium based denitration catalyst only can be recovered 30% left and right after testing, and regeneration effect is not fine.
Summary of the invention
The objective of the invention is in order to solve existing vanadium titanium based denitration catalyst regeneration effect is not good technical problem, in order to address this problem, we have designed a kind of two cleaning and regeneration methods of processing of vanadium titanium based denitration catalyst, realized the highly efficient regeneration of vanadium titanium based denitration catalyst, vanadium titanium based denitration catalyst denitration rate after regeneration can reach 87%, effectively reduces simultaneously SO
2/ SO
3Conversion ratio, greatly saved the denitration cost.
Concrete technical scheme of the present invention is: a kind of two cleaning and regeneration methods of processing of vanadium titanium based denitration catalyst, and the cellular vanadium titanium based denitration catalyst of inactivation is processed and made its activity recovery, comprise the following steps:
A, prepare air-ozone mist, standby;
B, the cellular vanadium titanium based denitration catalyst of inactivation is placed in the catalyst regeneration reactor;
C, air-ozone mist is filled with in the catalyst regeneration reactor, carries out oxidation processes, the vanadium titanium of must regenerating based denitration catalyst;
Key is: described method is further comprising the steps of:
D, Kaolinite Preparation of Catalyst active liquid, standby;
E, the regeneration vanadium titanium based denitration catalyst of step c gained is dropped in the catalyst activity liquid of steps d gained, flood taking-up after 4 ~ 6 hours, through the dry air dryings of 50 ~ 60 ℃ 1 ~ 3 hour, and then repeat once;
F, with vanadium titanium based denitration catalyst roasting 1 ~ 3h under the condition of 160 ~ 200 ℃ of step e gained, roasting 1 ~ 3h under the condition of 300 ~ 400 ℃ then, obtain the vanadium titanium based denitration catalyst of cleaning and regeneration.
The invention has the beneficial effects as follows: after catalyst activity immersion stain, the oxygen on vanadium titanium based denitration catalyst surface, titanium, vanadium atom concentration are compared obvious raising with the concentration of the corresponding atom of vanadium titanium based denitration catalyst of inactivation, improved the redox ability of vanadium titanium based denitration catalyst, the denitration rate can reach 87%, realized highly efficient regeneration, and the poisoning material of vanadium titanium based denitration catalyst reduces in a large number, active material increases, active in raw catelyst, while SO
2/ SO
3Conversion ratio also lower than the guarantee value of raw catelyst, greatly saved the denitration cost.
The specific embodiment
A kind of two cleaning and regeneration methods of processing of vanadium titanium based denitration catalyst, process and make its activity recovery the cellular vanadium titanium based denitration catalyst of inactivation, comprises the following steps:
A, prepare air-ozone mist, standby;
B, the cellular vanadium titanium based denitration catalyst of inactivation is placed in the catalyst regeneration reactor;
C, air-ozone mist is filled with in the catalyst regeneration reactor, carries out oxidation processes, the vanadium titanium of must regenerating based denitration catalyst;
Key is: described method is further comprising the steps of:
D, Kaolinite Preparation of Catalyst active liquid, standby;
E, the regeneration vanadium titanium based denitration catalyst of step c gained is dropped in the catalyst activity liquid of steps d gained, flood taking-up after 4 ~ 6 hours, through the dry air dryings of 50 ~ 60 ℃ 1 ~ 3 hour, and then repeat once;
F, with vanadium titanium based denitration catalyst roasting 1 ~ 3h under the condition of 160 ~ 200 ℃ of step e gained, roasting 1 ~ 3h under the condition of 300 ~ 400 ℃ then, obtain the vanadium titanium based denitration catalyst of cleaning and regeneration.
Described steps d is to take percentage by weight to be respectively 7 ~ 10%, 16 ~ 20% penetration enhancer and surface-active emulsifiers, be dissolved in percentage by weight and be 40 ~ 50% deionized water for stirring even, and then add percentage by weight to be respectively 6 ~ 10%, 11 ~ 15%, 6 ~ 8% ammonium metavanadate, ammonium paratungstate and ammonium paramolybdate, mechanical agitation mixed it in 25 ~ 35 minutes, obtain active supplementary liquid, supplement in liquid and add oxalic acid in activity, regulate pH value to 4 ~ 6, and with mechanical agitation, it was mixed in 2 ~ 4 minutes, place ageing 1 ~ 3h, obtain catalyst activity liquid.
Described step c is to be the air-ozone mist of 160 ~ 200mg/L with concentration, is filled with in the catalyst regeneration reactor oxidation processes 50 ~ 70 min under the condition of 10 ~ 20 ℃, the vanadium titanium of must regenerating based denitration catalyst with the flow velocity of 2 ~ 4m/min.
Described penetration enhancer is the Laurocapram of 0.1 ~ 0.5mol/L, and surface-active emulsifiers is the benzyl dimethyl phenol polyethenoxy ether of 3 ~ 3.5mol/L.
The present invention is in the specific implementation:
One, with ozone, the cellular vanadium titanium based denitration catalyst of inactivation is tentatively regenerated:
At first utilize ozone generator to prepare air-ozone mist standby, then the cellular vanadium titanium based denitration catalyst of inactivation is placed in the catalyst regeneration reactor, under 15 ℃, it is the air-ozone mist of 180mg/L with ozone concentration, with the flow velocity of 3m/min, in gas flowmeter injecting catalyst regeneration reactor, after oxidation processes 60min, close down ozone generator, vanadium titanium based denitration catalyst obtains regenerating.
Two, the preparation of catalyst activity liquid:
In the present invention, the specific embodiment of catalyst activity liquid is as shown in table 1:
Table 1
Take the benzyl dimethyl phenol polyethenoxy ether 268.8g of Laurocapram 126.66g, the 3.2mol/l of 0.3mol/L, be dissolved in the 660g deionized water, stir and it was mixed in 2 minutes, and then add ammonium metavanadate 120g, ammonium paratungstate 192g and ammonium paramolybdate 100g, mechanical agitation mixed it in 30 minutes, obtain active supplementary liquid, supplement in liquid and add oxalic acid in activity, regulate pH value to 5, and with mechanical agitation, it was mixed in 3 minutes, place ageing 2h, obtain catalyst activity liquid.
Three, carry out impregnation process with catalyst activity liquid:
With catalytic rate at 35% regeneration vanadium titanium based denitration catalyst (150 ~ 150 * 1000), be immersed in 10000g catalyst activity liquid, take out after 5 hours, through dry 2 hours of 55 ℃ of dry airs, dropped into again in catalyst activity liquid dipping 5 hours, and took out through 55 ℃ of dry airs dry 2 hours again, then through 180 ℃ of roastings 2 hours, 350 ℃ of roastings 2 hours, obtain the vanadium titanium based denitration catalyst of cleaning and regeneration.
Four, performance test:
It is 10 ~ 20 purpose particles that the vanadium titanium based denitration catalyst of cleaning and regeneration is crushed to particle diameter, measure the activity of vanadium titanium based denitration catalyst, and the activity of the vanadium titanium based denitration catalyst after processing with conventional process modes such as pickling, washings respectively compares.
Respectively the vanadium titanium based denitration catalyst of three kinds of regeneration preparations is put into fixedly tubular reactor, with simulated flue gas and reducing agent NH
3(NH
3=0.2%, CO
2=3%), at air speed=40000h
-1Under test condition, pass into fixedly in tubular reactor, the nitrous oxides concentration that detects fixedly tubular reactor import and export with flue gas analyzer is respectively NO
Advance, NO
Go out, denitration rate η=(NO
Advance-NO
Go out)/NO
Advance* 100%, test result is as shown in table 2:
Table 2
| Renovation process | Washing | Pickling | Two processing |
| Denitration rate η | 12% | 46% | 87% |
, by as seen from Table 2, can reach 87% through pair denitration rate of the vanadium titanium based denitration catalyst that processing cleaning and regeneration methods make, apparently higher than the denitration rate of the vanadium titanium based denitration catalyst of processing through pickling, washing.Through pair vanadium titanium based denitration catalyst that processing cleaning and regeneration methods make, oxygen, titanium, the vanadium atom concentration on surface are compared obvious raising with the concentration of the corresponding atom of inactivation vanadium titanium based denitration catalyst, reached the purpose that regeneration is processed, and the poisoning material of vanadium titanium based denitration catalyst reduces in a large number, active material increases, vanadium titanium based denitration catalyst activity is higher than raw catelyst, simultaneously SO
2/ SO
3Conversion ratio also lower than the guarantee value of raw catelyst, greatly saved the denitration cost.
Claims (4)
1. two cleaning and regeneration methods of processing of a vanadium titanium based denitration catalyst, process and make its activity recovery the cellular vanadium titanium based denitration catalyst of inactivation, comprises the following steps:
A, prepare air-ozone mist, standby;
B, the cellular vanadium titanium based denitration catalyst of inactivation is placed in the catalyst regeneration reactor;
C, air-ozone mist is filled with in the catalyst regeneration reactor, carries out oxidation processes, the vanadium titanium of must regenerating based denitration catalyst;
It is characterized in that: described method is further comprising the steps of:
D, Kaolinite Preparation of Catalyst active liquid, standby;
E, the regeneration vanadium titanium based denitration catalyst of step c gained is dropped in the catalyst activity liquid of steps d gained, flood taking-up after 4 ~ 6 hours, through the dry air dryings of 50 ~ 60 ℃ 1 ~ 3 hour, and then repeat once;
F, with vanadium titanium based denitration catalyst roasting 1 ~ 3h under the condition of 160 ~ 200 ℃ of step e gained, roasting 1 ~ 3h under the condition of 300 ~ 400 ℃ then, obtain the vanadium titanium based denitration catalyst of cleaning and regeneration.
2. two cleaning and regeneration methods of processing of a kind of vanadium titanium based denitration catalyst according to claim 1, it is characterized in that: described steps d is to take percentage by weight to be respectively 7 ~ 10%, 16 ~ 20% penetration enhancer and surface-active emulsifiers, be dissolved in percentage by weight and be 40 ~ 50% deionized water for stirring even, and then add percentage by weight to be respectively 6 ~ 10%, 11 ~ 15%, 6 ~ 8% ammonium metavanadate, ammonium paratungstate and ammonium paramolybdate, mechanical agitation mixed it in 25 ~ 35 minutes, obtain active supplementary liquid, supplement in liquid and add oxalic acid in activity, regulate pH value to 4 ~ 6, and with mechanical agitation, it was mixed in 2 ~ 4 minutes, place ageing 1 ~ 3h, obtain catalyst activity liquid.
3. two cleaning and regeneration methods of processing of a kind of vanadium titanium based denitration catalyst according to claim 1, it is characterized in that: described step c is to be the air-ozone mist of 160 ~ 200mg/L with concentration, flow velocity with 2 ~ 4m/min is filled with in the catalyst regeneration reactor, oxidation processes 50 ~ 70 min under the condition of 10 ~ 20 ℃, the vanadium titanium of must regenerating based denitration catalyst.
4. two cleaning and regeneration methods of processing of a kind of vanadium titanium based denitration catalyst according to claim 2, it is characterized in that: described penetration enhancer is the Laurocapram of 0.1 ~ 0.5mol/L, and surface-active emulsifiers is the benzyl dimethyl phenol polyethenoxy ether of 3 ~ 3.5mol/L.
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Cited By (7)
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|---|---|---|---|---|
| CN103920540A (en) * | 2014-04-17 | 2014-07-16 | 宁波大学 | Method and device for regenerating SCR (Selective Catalytic Reduction) denitration catalyst applied to aftertreatment of diesel engine exhaust |
| CN104492507A (en) * | 2014-12-25 | 2015-04-08 | 宜兴国电精辉环保设备有限公司 | Regeneration method of fluorine poisoning waste denitration catalyst |
| CN104815707A (en) * | 2015-05-07 | 2015-08-05 | 中国华能集团清洁能源技术研究院有限公司 | Inactivated vanadium-titanium-based honeycomb-like denitration catalyst low-temperature modifying regeneration liquid and preparation method thereof |
| CN105148940A (en) * | 2015-08-20 | 2015-12-16 | 天河（保定）环境工程有限公司 | Regeneration impregnation liquid and regeneration technology for vanadium-titanium corrugated plate type denitrification catalyst |
| CN105521831A (en) * | 2015-12-16 | 2016-04-27 | 杭州海韵环保工程有限公司 | Regeneration technology of marine vanadium-titanium catalyst for SCR denitrification |
| CN105728064A (en) * | 2016-03-04 | 2016-07-06 | 北京科林佰德化工科技有限公司 | Method for cleaning and regenerating SCR denitration catalyst for potassium and sodium poisoning deactivation |
| CN108671967A (en) * | 2018-05-22 | 2018-10-19 | 马鞍山钢铁股份有限公司 | A kind of solvent heat green high-efficient regeneration method of sintering flue gas failure SCR denitration |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103920540A (en) * | 2014-04-17 | 2014-07-16 | 宁波大学 | Method and device for regenerating SCR (Selective Catalytic Reduction) denitration catalyst applied to aftertreatment of diesel engine exhaust |
| CN103920540B (en) * | 2014-04-17 | 2015-11-25 | 宁波大学 | The renovation process of SCR denitration and device in a kind of diesel exhaust aftertreatment |
| CN104492507A (en) * | 2014-12-25 | 2015-04-08 | 宜兴国电精辉环保设备有限公司 | Regeneration method of fluorine poisoning waste denitration catalyst |
| CN104492507B (en) * | 2014-12-25 | 2016-08-17 | 宜兴国电精辉环保设备有限公司 | The renovation process of fluorosis waste denitration catalyst |
| CN104815707A (en) * | 2015-05-07 | 2015-08-05 | 中国华能集团清洁能源技术研究院有限公司 | Inactivated vanadium-titanium-based honeycomb-like denitration catalyst low-temperature modifying regeneration liquid and preparation method thereof |
| CN104815707B (en) * | 2015-05-07 | 2017-12-08 | 中国华能集团清洁能源技术研究院有限公司 | One kind inactivation vanadium titanium-based Faveolate denitration catalyst low temperature modification regenerated liquid and preparation method thereof |
| CN105148940A (en) * | 2015-08-20 | 2015-12-16 | 天河（保定）环境工程有限公司 | Regeneration impregnation liquid and regeneration technology for vanadium-titanium corrugated plate type denitrification catalyst |
| CN105521831A (en) * | 2015-12-16 | 2016-04-27 | 杭州海韵环保工程有限公司 | Regeneration technology of marine vanadium-titanium catalyst for SCR denitrification |
| CN105728064A (en) * | 2016-03-04 | 2016-07-06 | 北京科林佰德化工科技有限公司 | Method for cleaning and regenerating SCR denitration catalyst for potassium and sodium poisoning deactivation |
| CN108671967A (en) * | 2018-05-22 | 2018-10-19 | 马鞍山钢铁股份有限公司 | A kind of solvent heat green high-efficient regeneration method of sintering flue gas failure SCR denitration |
| CN108671967B (en) * | 2018-05-22 | 2021-03-19 | 马鞍山钢铁股份有限公司 | Solvent heat green efficient regeneration method of sintering flue gas failure SCR denitration catalyst |
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Application publication date: 20131113 |